Fluorinated polyhedral oligomeric silsesquioxane (“F-POSS”) molecules are a subclass of polyhedral oligomeric silsesquioxanes (“POSS”) which consists of a silicon-oxide core [SiO1.5] with a periphery of long-chain fluorinated alkyl groups. F-POSS molecules possesses one of the lowest known surface energies leading to the creation of superhydrophobic and oleophobic surfaces. A feature of F-POSS material is that it ordinarily forms a siloxy cage that acts like an inorganic glass-like material, but have organic R group substituents at the matrix apices, which provides unusual properties and applications. See Formula I below.

F-POSS molecules find application in material science. For example, superhydrophobic and superoleophobic surfaces have been produced using F-POSS, either cast on a substrate or blended into a polymer matrix. See for example Chhatre, S. S.; Guardado, J. O.; Moore, B. M.; Haddad, T. S.; Mabry, J. M.; McKinley, G. H.; Cohen, R. E. ACS Appl. Mater. Interfaces 2010, 2, 3544-3554; Mabry, J. M.; Vij, A.; Iacono, S. T.; Viers, B. D. Angew. Chem., Int. Ed. 2008, 47, 4137-4140; Tuteja, A.; Choi, W.; Mabry, J. M.; McKinely, G. H.; Cohen, R. E. Proc. Natl. Acad. Sci. U.S. Pat. No. 2,008,105, S18200/1S18200/29; and Tuteja, A.; Choi, W.; Ma, M.; Mabry, J. M.; Mazzella, S. A.; Rutledge, G. C.; McKinley, G. H.; Cohen, R. E. Science 2007, 318, 1618-1622.
Preparation of functionalized F-POSS molecules has been achieved with limited success. Early approaches involved the preparation of incompletely condensed silsesquioxanes. The most effective early approaches have involved the opening of completely condensed POSS cage edges by acid catalysis and isolation of disilanol fluorinated polyhedral oligomeric silsesquioxane (F-POSS-(OH)2). The isolated F-POSS-(OH)2 molecule has been subsequently treated with dichlorosilanes of the type Cl2SiR1R2 to produce functionalized F-POSS structures. See, Ramirez, S. M.; Diaz, Y. J.; Campos, R.; Stone, R. L.; Haddad, T. S.; Mabry, J. M. J. Am. Chem. Soc., 2011, 133, 20084-20087. A major drawback of such approaches is the difficulty in isolating the desired disilanol. Without being bound by theory, it is postulated that the completely condensed F-POSS cage exists in equilibrium with the ring-opened disilanol product under acidic conditions. Accordingly, the ring-opened disilanol is constantly undergoing condensation to the lower energy state of the completely condensed F-POSS cage. The instability of the disilanol intermediate results in low overall yields of functionalized F-POSS molecules, typically in the range of 25%-35% from the starting completely condensed F-POSS starting material.
It would be desirable to provide an efficient, high-yield process for producing functionalized F-POSS molecules for use in materials.